Plant response agents



Patented May 5, 1953 UNITED STATES PATENT OFFICE iPLANTRESPONSE AGENTS Nathaniel .Tischlerl Pahnyra, N. J 'assignor to Sharples Chemicals lnc a corporation of Delaware 1 No'DraW iIig Application June 13, 1951,

. Serial No. 231,441

of the aforesaid acids, and particularly 3,6-en-u dOXO 12,3,6 tetrahydro orthophthalic acid and/or 3,6-endoxohexahydro-orthophthalic acid, per se or in equivalent form, and more .particu-. larly the exo-cis isomers, are highly effective for the purpose, and it is a feature of this invention to provide compositions containing the above active ingredients in admixture With simple, readily available materials which enhance, or-intensify the plant response activity of the above active'ingredients. These andother features will become apparent to persons skilled in the'art as thespecification proceeds.

(Jo-pending application Serial No. 81,026, filed March 11, 1949, by Nathaniel Tischlerand Ernest P. Bell, which has matured into Patent No. 2,576,080, granted November 20, l95l, teache s the eificacy of the 3,6-endoxohydro-orthophthalic acids and their derivatives in bringing about useful plant response effects such as leafabsciss'ion (partial or complete), blossom thinning, vine kill, total destruction of the plant, adventitious root formation, or delay of fruit drop, the particular plant response manifested depending to a large extent upon the applied concentration of the responseagen't, and'the species and degree of maturity of theplant undergoing treatment. The use of 3,6-endoxchexahydro-orth'opnthalic acid, per se or in equivalent form, forthe above purposes is particularly described and claimed'in the co-pending application of Ernest PJBelI-an'd Nathaniel Tischler, Serial No. 131,561, filed De cember 6, 1949, noW'Pat'ent No. 2,576,081, granted November 20, 1951; and theme of '3;6endoxo l,2,3,6-tetrahydro-orthophthalic acid, per se or in equivalent form, for such purposes is particularly described and claimed in the co-pending application of the same inventors, Serial No. 131,502, filed December 6, 19 19, now Patent No. 2576;032, granted November 2 3, 1951. Both 'of these applications are continuaticns4n-part of said firstmentionedapplication.

The. above-mentioned compounds as applied tof' plantsmay be in the'form of the acid per s'eor in '17 Claims. (01. 71-25) otherfo'rm, such a's'inthe'formof the anhydride andXor-a salt-which contains the corresponding anion or anions of ortho configuration, the same as in the case of the acid per se, said anion or anions being either acid or neutral in character, in-chemical combination with a sufiiciency of cation or cations "to satisfy valencerequirements, such as one o'r'more metal and/or metalloid cations such as sodiumpota'ssium, calcium, strontium, magnesium, aluminum, iron, ccbalt, nickel,

"zinc, cadmium, mercury, copper, ammonium,

mono-,diand trialkylarnmonium, mono-, diand 'trialkanolammonium, and mixed -a1kylalkanolammohium which is N-substituted by from 2 to 3 radicals o'fthe type indicated.

Thus the acid is the active materiaL-and this is true vvhether'it is used as such, orin the form of a salt, or anhydride, or other equivalent form.

of at least-6.1 %'-"by' 'weight, and still more particulafly'of at least 1% by Weight.

Watersolubilityis "desirable so that anions (acid or "neutral or'botl i) are formed when the acids, per se or in chemically equivalent form, are dissolved in water. The desirahilit v" of. suchanions will presently become apparent.

Acid anion's'nia'y be theoretically illustratedoy r'eferenceto the acid'3,6 endoxohexahydro-orthophthalate "anionjby'which is meant a univalent anion having a structure defined a by the formula JCH-( -O "CH2 us on 0 wherein X is a cation, considered by "modern Neutral anions i may be theoretically illustrated by reference to the neutral 3,6-endoxohexahydrocrthophthalate anion by which is meant a divalent anion having a structure defined by the Theoretically, similar anions are formed when the tetrahydro acid or its chemically equivalent forms are dissolved in water.

Thus the foregoing active ingredients may be defined as compounds which when in the presence of water yield anions having the configuration in which Y represents one of the group consisting of an unsatisfied valence and a cation, and in which R represents one of the group con; sisting of the vinylene radical and the ethylene radical.

Although the present applicant does not wish to be bound by any particular theory as to .the mechanism whereby useful plant response effects are produced,- a considerable amount of experimentation strongly indicates that s aid effacts are brought about by the existence in aque ous media of anion or anions (acid and/or neutral) of the type illustrated above. Both neutral anion and acid anion are eifective. feature of this theory is that the acid or acids A salient 1 the term carbon-to-carbon linked is meant that each carbon atom is linked to at least one other carbon atom.

Examples of hydroxy, carboxylic acids of the foregoing kind are glycolic acid, lactic acid, hydracrylic acid, the various hydroxybutyric and hydroxyvaleric acids, epsilon-hydroxycaproic acid, alpha, gamma-dihydroxybutyric acid, glyceric acid, tartronic acid, malic acid, tartaric acid, citramalic acid, and citric acid.

Examples of salts of such hydroxy acids are ammonium salts, including neutral ammonium salts, as well as ammonium acid salts such as of the dicarboxylic acids, and such as diammonium hydrogen and ammonium dihydrogen salts in the case of tricarboxylic acids; mono-,

'di-, and trialkylammonium salts, having from of the invention, when applied per se, or in equivalent form, to a living plant, makes the desired anion or anions (acid and/or neutral) available to the plant, at or near the siteof application, and through translocation phenomena, at points far removed from thesite of application.

The desired anion or anions are made available by virtue of the fact that the acids per se, and their equivalent forms, are water-soluble and ionizable. Therefore, when such acornpound is absorbed into the vascular system of a same or different.

1 to 4 carbon atoms in each alkyl radical; mono-,

diand trialkanolammonium salts having from 2 to 3 carbon atoms in each alkanol radical; and mixed alkylalkanolammonium salts which are N -substituted by from 2 to 3 radicals of the type and carbon content indicated. Thev substituted ammonium salts include both neutral and acid salts, wholly analogous to the ammonium salts such as are mentioned above. 4 In the case of salts containing more than one ammonium and/or substituted ammonium radicals (i. e., cations), said cations may be the The preparation of the salts falling within the scope of the invention may be accomplished by any means known to the art, such as by neutralization of a selected acid with the requisite amount of the selected base or mixture of bases. In general, water is an excellent liquid medium for carrying out such neutralizations, although at times the use of other media may be desirable.

Likewise, the preparation of the 3,6-endoxohydro-orthophthalic acids, per se and in equivalent form, may be accomplished by any means known to the art, and suitable methods will sug plant, it dissolves in the aqueous plant juices and provides the functioning anion or anions. The resulting-physiological activity is believedto be ascribable to the presence of said anionor anions.

The acids per se and their equivalent forms may thus be regarded as very convenient media for furnishing the desired anion or an-.

ions to susceptible portions of the plant.

It follows, therefore, that theacids per. se and:

their equivalent forms are equally usable.

The foregoing compounds are highly effective for the intended purpose.

I have discovered that the amount of the respective compounds used to produce a given plant response effect may be markedly reduced, or the plant response effect obtained with a given amount of active ingredient markedly increased, by admixing with anysaidcompound or compounds, one or more saturated, openchain, carbon-to-carbon linked, monoand di hydroxy, mono-, diand tricarboxylic acids having from 2 to 6 carbon atoms, and their ammonium and substituted ammonium salts; said salts being either in neutral or acid form. Par.-

ticular-substituted ammonium salts are the-ah kylammonium salts, alkanolammonium --salts,,-.

and mixedv 'alkylalkanolammonium,saltsl By intensifier is in solid form, or while in solution in a common solvent such as water. In the latter case the solution may be marketed such, or if desired, may be dried, such as by spray or drum drying, particularly when the in tensifier is normally solid. In any case, it is preferred to have any solid admixture in finely divided form and sufiiciently dry to be free flow- 111g.

The admixtures are applied to the crop or plants in any desired manner, such as in the form of a solid, for example, by dusting, or in the form ofa liquid, for example, by spraying.

Compositions may be formulated by mixing the admixture containing the intensifier and active' ingredient with any desired liquid or solid carriers, such asany of the finely divided solid carriers known inthe dusting art, which are preferably of large surface area; such-as clay, for example, fullers-earth;.pyrophyllite, talc, ben' tonite, kieselguhr, diatomaceousearth, etc. Any of the commercial clays' available'on the market in finely divided form maybe used, and particularly those which are normallyemployed as insecticide carriers. Commercial clays, it will be understood. are generally identified by trade names (reflecting the source and mode of processing), of which Homer Clay, Celite, and Tripoli may be mentioned as typical.

Non-clay carriers which may be formulated with my admixture include, for example, sulfur, volcanic ash, calcium carbonate, lime, by-product iignin, li'gnocellulose, flour, such as wood, walnut shell, wheat, soybean, potato, cottonseed, etc. I

Any desiredmixturemay be prepared by any suitable method; Thus; he solid, the active ingredient may be ground to a fine powder and tumbled together with the" intensifier, particularly when in solid "form, although liquid forms may be employed to a certain degree in producing free-flowing solid admixturesor the intensifier and the active ingredient may be ground together; alternatively, the active'ingredient in liquid form, including solutions, dispersions, emulsions,and'suspensions thereof, may be admixed'with the intensifier in finely divided form in amounts small-enough to preserve the freeflowing property of the final dust composition, and vice versa. Or excess liquid may be removed, such' as by vaporization, for example, under reduced pressure. The same-applies to mixtures of the active ingredient, the intensifier. and any finely divided solid'carrier and/or other material.

When solid compositionsare employed, in or der to obtain a high degree-of plant coverage with minimum'poundage per acre, it is desirable that the-composition bein finely divided form. Preferably, the dust containin'gthe active ingredient sho'uldbe sufliciently fine that substantially all will pass through a 50 mesh sieve, and more particularly through a 200 mesh sieve. Excellcnt results have beenobtained in which the dust composition is comprised predominantly of particles in the range from 15 170 microns.

Finer dusts, such as those consisting largely of particles in the. range of S-microns and below have excellent covering capacity but are somewhatmore subject to drift and are moreexpensive to prepare.

For spray application. the admixture may be dissolved ordispersed .in-a liquid carrier such as water orother suitable liquid.-

A ueoussolutions or dispersions are economical and desirable. In general, the choice of the particular liquid carrier employed will be-guided somewhat by prevailing circumstances, such as its availability, its solubility or'dispersion characteristics toward the particular. admixture employed, and/or its toxicity toward the plants undergoing treatment. In general, water is an excellent liquid carrier.

Thus, spray formulations comprising the active ingredient in theform of a solution, suspension, dispersion, or emulsion, in aqueous or non-aqueous media may be employed.

Emulsionsor dispersions of the admixture inthe liquid carrier may be prepared by. agitation of the admixture with the carrier. This iscommonly done at the time of spraying: Preferably, however, the agitation should take place in the presence of an emulsifying .ordispersing' agent (surface-active agent), in order to facilitate the" preparation of said emulsion or dispersion;

Emulsifying and dispersing agents are well known in the art, and include, for example, fatty alcohol sulfates, such as sodium lauryl sulfate, aliphatic or aromatic sulfonates, such as sulfonated castor oil or the various alkaryl sulfonates (such as the sodium salt of monosulfonated nonyl naphthalene or tertiary dodecyl benzene), and non-ionic types of emulisfying and dispersing agents such as'the high molecularweight alkyl 'polyglycolethers or analogous thicethers such as the decyl, dodecyl and tetradecyl polyglycolethers and thioethers containing from 25to '75 carbon atoms.

The use, if desired, of a'djuvants, such as wetting agents and/or humectants (water-retaining agents), is also contemplated in connection with solutions of the admixture, such as-water'solue- Any suitable wetting agentand/orhu trins such as white dextrin, canary dextrin,-

British gum, etc, honey, molasses, maple syrup, maple sugar, and starch syrups such as corn syrup, etc.

For adjuvant purposes, any desired quantity of wetting agent may be employed, such as up to 250% or more based on active ingredient. For wetting purposes, the amount of adjuvant used may be considered'to be that required to impart the desired wetting qualities to the spray solution. as formulated, such as approximately 0.05% by Weight of the spray solution. The use of considerably larger-amounts is not based upon wetting properties, although present, but is a function. of the physiological behavior of the wetting agent after spraying upon the plant.

It should be considered that once the solution has been. sprayed upon the plant, the concentration of wetting agent existing upon the plant is in no sense a function of the concentration existing in the original spray solution. Thus, evaporation might concentrate the Wetting agent considerably, or the presence of dew on the plant surfaces, or'of plant juices on the plantL surfaces might considerably dilute this agen It will, of. course, be'understood that wetting agents, particularly in solid form, may be compounded with the admixture when in solid form.

Although the admixture of active ingredient and intensifier may be applied to the growing plant in concentrated form, it is usually desirable to empioy liquid or solid formulations, for example, as discussed above, in which the active ingredient constitutes less than 36% by weight of the total, such as less than 10% and even as low as 0.1

Other substances than the carrier, surface active agent, and/or humectant may be included in solid or liquid formulations ii desired. Thus, active ingredients other than those disclosed herein. and compatible with the admixture may be added if desired for any particular purpose. Also substances may be added to bring about various physical improvements such as the prevention of lumping during storageQorimprove ment with respect to coverage, moisture adsorption, adherence, etc. Such other active ingredients may be included in said formulations to accomplish various physiological effects. For example, it may at times be expedient to include singly or in combination, substances such as fungicides,insecticides, bactericides, or types of plant response agents other than those agents discussed herein.

In practice of the process as applied to defoliation, the rate of application (i. e. the amount of admixture per cropunit) for best results will depend among other factors upon the species of plants being treated and upon their maturity. In any event, the amount of active ingredient employed for the same plant response effect will be substantially lower than whenthe intensifier is not present.

As a rule the more mature the plant at the time of application, the less active material is required. In practice, the crop is normally treated for defoliation purposes, 1 or 2 weeks prior to harvesting. In some instances, more than one application may be desirable, especially if heavy rains or winds should occur soon after the application,or to obtain an accumulative effect. Then too, in order to avoid possible injury to any particular crop, it may be desirable for an inexperienced operator to apply the defoliant initially at a relatively low rate, and to follow with a second application if necessary after observation of the first effects, to obtain the degree of defoliation desired.

Use of dosages greatly in excess of the minimum required for good defoliation may result in shock to the plant with attendant injury to the remainder of the plant.

In fact, the plant response compositions of the present invention are effective herbicides when used in amounts substantially greater than those required for defoliation, and they may be used advantageously for the killing of plants or vines (as in the case of potatoes) when desired, such as, for the killing of undesired plants, for example, weeds or grasses, or for the killin of crops, irrespective of whether such undesired plants or crops are of species which lend themselves to defoliation.

Thus when defoliation is the objective the quantity applied should be sufficient to cause at least the major portion of the leaves to dry up and/or to drop from the living plant, but insuflicient to cause substantial herbicidal action on the plant. On the other hand, when plant killing is the objective, any amount sufficient for this purpose may be applied. In the latter connection, since different species of plants vary markedly in their relative resistance to herbicidal action, selective killing of plant species may be practiced. Such selectivity may be varied by compounding, such as with adjuvants, for example, wetting agents, in addition to the use of an intensifier.

I am aware of the fact that it has been proposed to use certain ammonium salts, such as ammonium sulfate, in combination with phenolic substances, such as dinitroalkylphenols and pentachlorophenol, for plant response purposes. The purpose of such use of ammonium salts as explained by Crafts and Reiber, Hilgardia, volume 16, pages 487-499, and by Crafts, Science, volume 108, pages 85-86, is to make available the free phenol at the plant surface from an aqueous solution of a Water-soluble salt of said phenol. The phenol in such cases is the active plant response substance and is continuously regenerated at the plant surface from its Water-soluble salt by virtue of the presence of the ammonium salt. -As the free phenol is absorbed by the plant surface, further free phenol is generated under equilibrium conditions. The plant response effect of the free phenol is not enhanced or intensified by such procedure, or in other words, is substantially the same as that obtained by the application directly to the plant of a similar quantity of free phenol. In view of the insolubility of the phenol in water, this procedure is adopted in order to make available the use of-water as a vehicle for applying the plant response agent, i. e. herbicide, to the plant surfaces.

In the case of my invention, on the other hand, the plantresponse efiect obtained from a given quantity of active ingredient is greater than that obtained by the application of the same quantity of the particular active ingredient to the plant in the absence of my intensifier. In fact, the plant response effect obtained with the same quantity of active ingredient may be increased many times by the addition of larger quantities of my intensifier. The intensification begins to manifest itself by the addition of a small proportion of my intensifier and increases to a point of optimum intensification by the addition of increasing proportions of intensifier. For optimum plant respflise efiects, the proportion of intensifier to active ingredient may varyv somewhat between specific active ingredients and between specific varieties of plants undergoing treatment, so that the exact proportion for optimum effect under all conditions cannot be given. However, the intensificaticn of the plant response efiect is present when a small quantity of intensifier is added, and the addition of intensifier beyond the point at which no further marked increase in intensification is obtained does no harm.

The exact mechanism by which the intensification of the above ingredient is obtained in the practice of my invention is not known. However, such intensification is cogently demonstrated by the following examples which are by way of illustration and not oflimitation.

Example 1 Three series of aqueous solutions of disodium 3,6-endoxohexahydro-orthophthalate were prepared, each series consisting of five solutions having the following respective concentrations of this active ingredient: 0.00125%, 0.0025%, 0.005%, 0.0075%, and 0.01%.

One series of solutions contained no intensifier. Each of the other two series contained, in addition to the active ingredient, a constant amount (0.05%) of an intensifier. The intensifiers emplayed in preparing the respective series of solutions were ammonium dihydrogen citrate and diammonium hydrogen citrate.

Thus the ratio of intensifier to active ingredient ranged from 5:1 to 40:1;

These solutions were applied to potted young Dwarf Horticultural bean plants which were about 8 inches high, and on which the first trifoliate leaf was large and the second trifoliate leaf was small. Separate groups of eight such plants were dipped to the first nodes into the respective test solutions of each series, and the.

excess solution was shaken off. Approximately 2 ml. of solution remained on each plant. Thus the dosages per plant of active ingredient, depending on the respective concentrations of the test solutions, were approximately 25, 50, 100, 150, and 200 micro rams. respectively. The dosage per plant of intensifier-was constanig-amounting to approximately 1000 micrograms.

One group of eight plants was not treated with any solution and was kept as a control.

Control tests using the intensifiers in the absence of active ingredientwere also conducted. Groups. of eight plants were treated with 0.05% aqueous solutions "of the respective intensifiers, using the above-described method of application.

All plants used for this testwere of the same age and had been grown at the same time and under thesame conditions. After the test was commenced, treated plants and untreated con trolswere again kept underthe same conditions and therefore .were subjected to comparable growing conditions.

Observations made three days after treatment are summarized in Tablet1.

Several symbols are employed in this table, their meanings being as follows in this example and wherever applicable in the other examples? lt;l ightly mod=moderately sev=severely bn=burned ret=retarded adh=adhering C=untreated control PL'=primary leaves Ts=trifoliate shoots 10 this active'ingredient: 0.001%, 0.0025%, 0.005%; 0.101 and 0.015%.

One series of solutions contained no intensifier. The otherseries contained, in addition to the active ingredient, a constant amount (0.05%) of an intensifier, methylammonium dihycirogen citrate.

Thustheratio of intensifier to active ingredient ranged from 3.3 :1 to 50 :1.

Separate groups of eight potted Dwarf Horticultural bean'plants at the stage at which the first trifoliateleaf was still furled were dipped to the first-nodes into the respective test solution of each series, and excess solution was shaken off. Approximately 22- ml. of solution remained on each plant. 'Ihus'the dosages per plant of active ingredient 'depending on the respective concentrations of the test solutions, were approximately 50; 100,200, and 300 micrograms, respectivelyl. The dosage per plant of intensifier was constant, amounting to approximately 1000 microrains.

All plants used for this test were of the same I .ageand had been grown at the same time under the same conditions. After the test was com- ...menced, treated plants, including the treated V controls, and the untreated controls were again kept under the same conditions and therefore were subjected to comparable growing conditions. Observations made four days later were as fol- Cone. of ective ingredient;

lows; Physiological effects Q With methylammonium Without intensifier dihydrogen citrate As 2B, 18; adh IIr-hiQd. hn; T ret.

do 4E, 48; adh PL-inod bn; '1Sn1od ret. 4B, 18; Eldh'PL'Ill0(1 8B; TS-sevi'et.

bn; lt net. 6B, 15; adli-Plrmod 3B, 43; adh PL-frozen;

bn; 'lS-mod ret. TS-sev ret. 6B, 2S;alh ILfrozen; 3B, 48; adh PLfr0Zcn;

TS-mod rot. TS-sev ret.

;, for example, means each of two plants had a single primary leaf abscised; 6B, for example, H means each of six plants had both primary leaves abscised.

Table 1 Theterm frozen as used to describe a condition of the leaves of aplant treated with a deffoliant .gdenotes that condition in which the leaves have undergone such a quick and drastic response PHYSIOLOGICALEFFECT Active ingredient pc'rplant intensifier i 25 micrograms 50 micrograms j'IUD-micrograms micrograms 200 micrograms AS As PLltbn;lS- PL-mod bn; 4B; adh PL- None as O. TS-It ret. lmod bn; lS

ret. Hi (1 g PL--ltbn;l'lS 3B, 15; adh 3B, 38; adli 6B, 28; adh 8B; 'ISscv ret. ili fg (1 y m an as C. PLlt bn; ILm,ocl bn y PL,-mod bn;

i 'L 1B 3 "21 h 2I; s in B s dh l d en PLltbn:lS- 1B; adi P a l; a 5 l; a ciFr EQ 0 mg as C. lt-bn; 'lSlt PL-mod bn, -PL-mod bn; PLmod bn;

ret. '1Slt re TSmod ret. TS--sev rct.

Those plants which were not treated and those 5,

plants which were treated only with the intensifiers were entirely uninfected Similar control tests were conducted in the succeeding examples, and in no case was any effect noted on the plants.

EXAMPLE 2,

'Two series of aqueous solutions of disodium. 3,;6-endcxohexahydro-orthophthalate were pre-, pared, each series consisting of five solutions having the following respective concentrations of 76 that no absci'ssion layer has formed. The leaves then cling tenaciously to the plant although the leaf blade and petiole are dead and shriveled, and show-no tendency to abscise. Thus, it is to be understoodthat freezing of leaves indicates a more phytotoxic condition than when the leaves actually abscise.

v: EXAMPLE 3 TWO... se ies. of aqueous solutions of disodium 3,6-endoziohexahydroeorthophthalate were prepared, each series consisting of four solutions 11' having the following respective concentrations of this active ingredient: 0.001%, 0.0025%, 0.005%, and 0.01

One series of solutions contained no intensifier. The other series contained, in addition to the ac! tive ingredienta constant amount (0.05%) of an intensifier, diethylammonium dihydrogen citrate.

Thus the ratio of intensifier to active ingredient ranged from :1 to 50:1.

Separate groups of ten potted Dwarf Horticultural. bean plants at the stage at which the first trifoliate leaf was still furled were dipped to the first nodes into the respective test solutions of each series; and excess solution was shaken ofi. Approximately 2 ml. of solution remained on each plant. Thus the dosages per plant of active ingredient, depending on the respective concentrations of the test solutions, were approximately 20, 50, 100, and 200 micrograms, respectively.

first-trifoliate leaf was still furled were dipped to the first nodes'into the respective test. solutionsof each series, and excess solution was shaken oiT. Approximately 2 ml. of solution remained on each plant. Thus the dosages per plant of active ingredient, depending on the respective concentrations of the test solutions, were approximately 20, 50, 100, and 200 micrograms, respectively. The dosage per plant of intensifier was constant, amounting to approximately 1000 micrograms.

All plants used for this test'were of the same age and had been grown at the same time under the same conditions. After the test was commenced, treated plants, including the treated Physiological effects Cone. of active ingredient w h i h it tr et anolammo- Without intensifier mum dihydrogen citrate 0.001% PLltbn;TS-1tret. 6B, is; adh PLmod 0.0025% 4B, 23; adh PL-mod 8B; TS-sev ret.

bn; TS-mod ret.

0.005% 5B, 28; adli PL-mod 7B;adh PL-frozen;TS--

bn; TS-scv ret. sev ret.

0.0l%.. 7B,1S;adh PL-frozen; 6B; adh PL-irozen;

TSsev ret. TS-sev ret.

The dosage per plant of intensifier was constant. EXAMPLE 5 amounting to approximately 1000' micrograms,

All plants used for this test were of the same age and had been grown at the same time under the same conditions. After the test was commenced, treated plants, including the treated controls, and the untreated controls were'again kept under the same conditions and therefore were subjected to comparable growing conditions. Observations made 3 days later were as follows:

Physiological efiects Cone. of active ingredient Without intensifier With ,diethylammonium bn; TS-mod ret.

0.01% 10B; TS-scv rct 3B, 28; adh PLfrozen;

TS-3 plants sev dam aged, others sev ret.

EXAMPLE 4 Two series of aqueous solutions of disodium 3,6-endoxohexahydro-orthophthalate were prepared, each series consisting of four solutions the active ingredient, a constant amount (0.05%) of ammonium lactate as intensifier.

Thus the ratio of intensifier to active ingredient ranged from 6.6: l to 40:1.

Separate groups of eight potted Dwarf Horticultural bean plants at the stage at which the first trifoliate leaf was still furled were dipped to the first nodes into the respective test solutions of each series, and excess solution was shaken off. Approximately 2 ml. of solution remained on each plant. Thus the dosages per plant of active ingredient, depending on the respective concentrations of the testisolutions, were approximately 25, 50, 100, and micrograms, respectively. The dosage per plant of intensifier was constant, amounting to approximating 1000 micrograms. v

13 All plants used for this test were of the same age and had been grown at the same time under the same conditions. After the test was com menced, treated plants, including the treated controls, and the untreated controls were again kept under the same conditions and'therefore were menced, treated plants, including the treated controls, and the untreated controls were again kept under the same conditions and therefore were subjected to comparable growing conditions. servations were made 3 days after treatment, with results assummarized in Table 2.

Table 2 Physiological etfeets Active ingredient per plant Intensifler I micrograms micrograms 100 micrograms 150 micrograms None PL1tbn;'TS-as PLlt bru'TS-wsQ. 1B.1S;adhPL-ltbn; 2B, 3S; adli PL-mod Q ,TS-lt ret. bn; TS-lt ret.

Ammonium acid tartrate 2S; adh PL-mod bu; 9B, 2S;-*adh'PL- sev 6B, 63; adh PL- 9B, 28; adh PL'- TS-lt ret. bnyTS-mod ret. frozen; TS-sev ret. frozen; 'lS-sev rot.

Ammonium tartrate 1B, 3S; adh PL-mod 8B, 58; adh PL-sev 15B, 1S; adh PL-sev 10B, 68; adh PL- bn; TS,-1t ret. bn; TS-mod rct. bn; TS-sevret. frozen; ISscv ret.

EXAMPLE 7 subjected to comparable growing conditions. Oh servations made 4 days after treatment were:

Three series of aqueous solutions of disodium Physiological effects Oonc. of active ingredient Without intensifier With ammoniumlactatc EXAMPLE 6 Three series of aqueous solutions of disodium 3,6-endoxohexahydro-orthophtha1ate were prepared, each series consisting of four solutions having the following respective concentrations of this active ingredient: 0.00125%, 0.002573, 0.005%, and 0.0075%.

One series of solutions contained no intensifier. Each of the other two series contained,-in addition to the active ingredient, a constant amount (0.05%) of an intensifier, the particular intensifiers employed inpreparing the respective series of solutions being ammonium acid tartrate' and ammonium tartrate.

Thus the ratio of intensifier to active ingredient ranged from 6.6 :1 to 40:1.

Separate groups of 16 potted Dwarf Horticultural bean plants at the stage at which the first trifoliate leaf was still furled were dipped to'the first nodes into'the respective test solutions of each series, and excess solution was shaken off. Approximately 2 ml. or" solution remained oneach plant. Thus the dosages per plant of active ingredient, depending on the respective concentra-. tions of the test solutions, were approximately.

3,fi-endoxohexahydroeorthophthalate were pre-- pared, each series consisting of four solutions having the following respective concentrations of thisactive ingredient: 0.00125 0.0025 0.005 and 0.0075%.

One series of solutions contained no intensifier. Eachof the other two series contained, in addition to the active ingredienta constant amount (0.05%) of an intensifien The intensifier emplayed-in preparing the respective series of solutions were ammonium acid vmalate and ammonium malate.

Thustheratio of intensifier to active ingredient :rangeafrom 646:1 17014021. j

- Separate. groupsof eight potted Dwarfv Horti-t cultural bean plants at the stage at which the amounting to approximately 1000,1nicrogramaj I .All, plants used for this test were of means,

age and had been grown at the same time under;

the same conditions. After the test was commenced, treated plants, including the treated con-' trols, and theuntreated controls were again kept under the same condition and therefore weresubjected to comparable growing conditions;

with results as summarized in Table 3.

Active ingredient per plant Intensificr 25 micrograms 50 micrograms 100 micrograms 150 micrograms None PL-lt bn; TS-as C Ammonium acid malate PL-lt bn ISlt ret..

Pris-1t bu; TSas 0..

1B; 15; adh PLmod bn; lSlt ret. bn; 'lS-mod:rct. Ammonium malate PL-lt bn; TS-lt ret.. 2S; adh PL-mod bn; 5B, 28; adh PL;-mod 8B; TS-scv ret.

TS-lt ret. but 'IS-mod ret.

ammonium) 3,6-endoxohexahydro-orthophthalate were prepared, each series consisting of five;

solutions having the following respective molar concentrations of this active ingredient: 0.000025, H

0.00005, 0.001, 0.00025, and 0.005.

One series of solutions contained no intensifier. The other series contained, inaddition to the active ingredient, a constant amount (0.1%) of citric acid as an intensifier.

Separate groups of eight potted Dwarf Horticultural bean plants at the stage at which the first trifoliate leaf was still furled were dipped to the first nodes into the respective test solutions of each series, and excess solution was shaken off. Approximately 2 ml. of solution remained on each plant.

All plants used for this test were of the same age and had been grown at the same time under the same conditions. After the test was commenced, treated plants, including the treated controls (which were treated with a 0.1 %'isolution of citric acid in'water) and the untreated controls were again kept under the same conditions and therefore were subjected to comparable growing) conditions. Observations made eight days laterwere as, follows:

these three isomers the exo-cis isomer is preferred in view of its outstandingly greater activity. Furthermore, the exo-cis isomer can be pre-- pared more economically and conveniently. The endoxo ingredient in the foregoing examples was of the exo-cis isomeric form.

When the endoxo ingredients are used in the form of the acids per se and/or their anhydrides, aqueous solutions containing such acids and/or anhydrides probably contain non-ionized acid and/or anhydride in equilibrium with ionized material. Similar considerations might apply to some of the salts.

The alkylammonium salts of 3,6-endoxohydroorthophthalic acids, such as monoalkylammonium, dialkylammonium, or trialkylammonium salts preferably have from 1 to 12 carbon atoms in eachalkyl radical, the totality of carbon atoms preferably being not more than 12. The alkanolammonium salts such as monoalkanolammonium, dialkanolammonium, or trialkanolammonium preferably have from 2 to 3 carbon atoms in each alkanol radical. The mixed alkylalkanolammonium salts such as monoalkyl monoalkanolammonium, dialkyl 'monoalkanolammonium, or monoalkyl dialkanolammonium preferably have from 1 to 4 carbon atoms in each alkyl radical and from 2 to 3 carbon atoms in each alkanol radical.

00005.; 813, TS-scv ret.

phthalate, with no intensifier and with citric acid as an intensifier.

Both of these sodium salts without intensifier displayed approximately the same activity as the bis(triethylammonium) salt. Similarly, the ac tivity of the sodium salts was intensified by citric acid to about the same extent as in the caseof the bis(triethylammonium) salt.

The endoxo compounds are theoretically capa ble of existing in three separate and distinct geometrically isomeric .forms, namely, the exo-cis isomer, the endo-cis isomer, and the trans iso mer,-;

as defined in the case of the hexahydro= compounds by Woodward and Baer, Journal .of .the

American Chemical Society, '10, 1161 1166. "or 79;

The neutral and acid alkylammonium salts of the above-mentioned saturated, open-chain, carbon-to-carbon linked, monoand dihydroxy, mono-, diand tricarboxylic acids having from 2 to 6 carbon atoms, such as monoalkylammonium, dialkylammonium, or trialkylammonium salts, preferably have from 1 to 4 carbon atoms in each alkyl radical. The alkanolammonium salts such as monoalkanolammonium, dialkanolammonium, or .trialkanolammonium preferably have from 2 to 3 carbon atoms in each alkanol radical. The mixed alkylalkanolammonium salts such as monoalkyl monoalkanolammonium, dialkyl monoalkanolammonium, 0r monoalkyl dialkanolammonium preferably have from 1 to 4 carbon atoms in each alkyl radical and from 2 to 3 carbon atoms in each alkanol radical.

The following examples apply to both the active ingredient and the intensified Y Examples of monoalkylammonium salts are amass S, I post-emergencetreatment or cont ljol o f weeds, ulation am "omum salts df'suchjac Exam 16s" or trialkylanrnoriinm Sat; rimat y emmp mit i smm m mt py l" 111 11 23 1 diethanolam'monium, dipropanolammonium, eth anolpropanolammonium and similar salts of such Examples of" trialkanolainrn ni the triethanolammoniu m, tripro thanoldipropaiiol I old thanolarnmonium ands mil'a salts 'dfsuchacidsf Examples" of monoalk yl monoalkanolainmo nium salts are the methylethanolammonium, ethylethanolammoniuinj propylethanolammonium, butylethanolammonium, methylpropanolammonium, ethylpropanolammonium, propylpropanol- '1) amm n m, tyl p n a m ni m, n simi- 1. A composition prepared". for use as a plant Salts 0f such acids response agent Whichcomprises a compound se- Examples of dialkyl monoalkanolarnmonium m t from thefiroup j 'm of saturated,

salts are the dirnethylethanolammonium, diethm Opemchain, n gj h' mono and yletnanolammonium, dipropylethanolammonium, djhydroxy mono dii tricarboxync acids dibutylethanolammomum, dimethylpropanolamhaving from 2 to 6 carbon atoms, and salts f monium, diethylpropanolammonium, dipropylpropanolammonium, dibutylpropanolammonium, t yl t y t a a um, t yl t mixed alkylalkanol amines; and a compound panolammomum, ethyllampylethanolammonium, which when in the presence of water yields anions ethylpropyiprop-anolaminonium, propylbutylethahaving the onfigur ti n nolammonium, propylbutylpropanolammonium,

said acids with at least one of the group consisting of ammonia, alkyl amines, alkanol amines and and similar salts of such acids. E fi Examples of monoalkyl dialkanolammonium l CO- salts are the methyldiethanolammonium, ethyldiethanolammonium, propyldiethanolammonium, butyldiethanolammonium, methyldipropanolam- CH O monium, ethyldipropanolammomum, propyldi 1n WhlCh Y represents one of the group consisting propanommmgnium, butyldipropanolammonium, of an unsatisfied valence and a cation, and in methylethanolpropanolammonium, ethylethanolwhich R represelflts one Of the p consisting of propanolammonium pmpy1ethano1pmpan01am the vinylene radical and. the ethylene radlcal. moniurn, butylethanolpropanolammonium, and A compOSltlOn p epa ed for use as a plant similar lt of Such k; response agent comprising a compound which As pointed out above the salts contemplated when in the presence of Water yields o s of include both the acid salts and the neutral salts, x h x hy r -01'thophth 1ic a and as and mixed salts, that is salts in which the cations an intensifier therefor a compound selected from are different. the group consisting of saturated, open-chain,

The term plant as used herein is understood to carbon-to-carbon linked, monoand dihydro y include all portions of the plant, such as the roots, mono--, diand tricarboxylic acids having from 2 stems, leaves, blossoms, seeds, and fruits. 7 to 6 carbon atoms, and the salts of said acids with Among the plants which defoliate naturally at least one of the group consisting of ammonia, and which may be defoliated by the use of this alkyl amines, alkanol amines and mixed alkylinvention, are for example, cotton, potatoes, alkanol amines. tomatoes, and beans such as soybeans and lima 3. The composition of claim 2 in which the b ans, anions are of the exo-cis isomeric form.

4. The composition of claim 3 in which the intensifier is an ammonium citrate.

5. The composition of claim 3 in which the intensifier is an ammonium tartrate.

6. The composition of claim 3 in which the intensifier is an ammonium malate.

7. The composition of claim 3 in which the intensifier is ammonium glycolate.

8. The composition of claim 1 having admixed therewith a wetting agent.

9. The composition of claim 1 having admixed therewith a humectant.

10. A composition prepared for use as a plant response agent comprising a compound which when in the presence of water yields anions of 3,6 endoxo 1,2,3,6 tetrahydro orthophthalic acid; and as an intensifier therefor a compound selected from the group consisting of saturated, open-chain, carbon-to-carbon linked, monoand dihydroxy, mono-, diand tricarboxylic acids having from 2 to 6 carbon atoms, and the salts of said acids with at least one of the group consistin of ammonia, alkyl amines, alkanol amines and mixed alkylalkanol amines.

11. The composition of claim 10 in which the anions are of the exo-cis isomeric form.

12. The composition of claim 11 in which the intensifier is an ammonium citrate.

13. A method for regulating the growth characteristics of a plant, comprising applying to said plant a plant response composition comprising a compound selected from the group consisting of saturated, open-chain, carbon-to-carbon linked, monoand dihydroxy, mono-, diand tricarboxylic acids having from 2 to 6 carbon atoms, and the salts of said acids with at least one of the group consisting of ammonia, alkyl amines, alkanol amines and mixed alkylalkanol amines; and a compound which when in the presence of water yields anions having the configuration "3 if R/(l) CH-C- in which Y represents one of the group consist.-.

in which R represents one of the group consisting of the vinylene radical and the ethylene radical.

14. A method for inducing plant response in a living plant, comprising applying to said plant a composition comprising a compound which when in the presence of water yields anions oi 3,6 endoxohexahydro-orthophthalic acid, and a compound selected from the group consisting of saturated, open-chain, carbon-to-carbon linked, monoand dihydroxy, mono-, diand tricarboxylic acids having from 2 to 6 carbon atoms and the salts of said acids with at least one of the group consisting of ammonia, alkyl amines, alkanol amines and mixed alkylalkanol amines.

. 15. The method of claim 14 in which the anions are of the exo-cis isomeric form.

16. A method for inducing plant response in a living plant, comprising applying to said plant a composition comprising a compound which when in the presence of water yields anions of 3,6 endoxo 1,2,3,6 tetrahydro orthophthalic acid, and a compound selected from the group consisting of saturated, open-chain, carbon-tocarbon linked, monoand dihydroxy, mono-, diand tricarboxylic acids having from 2 to 6 carbon atoms, and the salts of said acids with at least one of the group consisting of ammonia, alkyl amines, alkanol amines and mixed a1- kylalkanol amines.

17. The method of claim 16 in which the anions are of the exo-cis isomeric form.

NATHANIEL TISCHLER.

No references cited. 

1. A COMPOSITION PREPARED FOR USE AS A PLANT RESPONSE AGENT WHICH COMPRISES A COMPOUND SELECTED FROM THE GROUP CONSISTING OF SATURATED, OPEN-CHAIN, CARBON-TO-CARBON LINKED, MONO- AND DIHYDROXY, MONO-, DI- AND TRICARBOXYLIC ACIDS HAVING FROM 2 TO 6 CARBON ATOMS, AND THE SALTS OF SAID ACIDS WITH AT LEAST ONE OF THE GROUP CONSISTING OF AMMONIA, ALKYL AMINES, ALKANOL AMINES AND MIXED ALKYLALKANOL AMINES; AND A COMPOUND WHICH WHEN IN THE PRESENCE OF WATER YIELDS ANIONS HAVING THE CONFIGURATION 